Tertiary-alkyl halocumyl peroxides

ABSTRACT

Tertiary-alkyl halocumyl peroxides of the formula   WHEREIN X is F, Cl, or Br; n 1-5; R is H, alkyl, cycloalkyl, or aryl; and R1 is tertiary-alkyl of 4-8 carbon atoms. These peroxides are useful for crosslinking polymeric materials without producing an objectionable odor.

United States Patent [1 1 Bafford [4 1 Oct. 14,1975

[ TERTIARY-ALKYL HALOCUMYL PEROXIDES [75] Inventor: Richard Anthony Bafford, Aiken,

[73] Assignee: Pennwalt Corporation, Philadelphia,

[22] Filed: Aug. 20, 1973 [21] Appl. No.: 389,769

Related US. Application Data [60] Division of Ser. No. 13,792, Feb. 25, i970, Pat. No. 3,755,464, which is a continuation-in-part of Ser. No. 77l,344, Oct. 28, I968.

[52] US. Cl. 260/861; 260/75 T; 260/80 C; 260/80.78; 260/88.2 S; 260/94.7 A; 260/94.9

GA; 260/DlG. 28

[51] Int. Cl. COSJ 3/24; COSK 5/14 [58] Field of Search... 260/86l, 75 T, 80 C, 88.2 S, 260/94.9 GA, DlG. 28, 94.7 A

[56] References Cited UNITED STATES PATENTS 3,234,)? 2/1966 Baum 260/93.7 3,257,346 6/1966 Gruver et al 260/23 3,435,060 3/1969 Ruchardt 260/453 8/1973 Bafford 260/610 R lO/l973 Gregorian et al. 260/610 R OTHER PUBLICATIONS Ballini et al., Chem. Abstr. 61, 8500g, (1964).

Primary ExaminerMelvin Goldstein Assistant Examiner-E. A. Nielsen Attorney, Agent, or FirmPlumley & Tyner wherein X is F, Cl, or Br; n l-5; R is H, alkyl, cycloalkyl, or aryl; and R is tertiary-alkyl of 48 carbon atoms. These peroxides are useful for crosslinking polymeric materials without producing an objectionable odor.

10 Claims, No Drawings TERTlARY-ALKYL HALOCUMYL PEROXIDES This is a division of application Ser. No. 13,792, filed Feb. 25, 1970, (now US. Pat. No. 3,755,464, which in turn is a continuation-in-part of copending application Ser. No. 771,344 filed October 28, 1968.

This invention relates to a novel tertiary-alkyl halocumyl peroxides, and more particularly, it relates to such peroxides which have an improved capability for crosslinking polymers and which do not at the same time produce an objectionable odor of acetophenone.

Many varieties of peroxides are known, including alkyl, cycloalkyl, and aralkyl peroxides. Typical of such compounds are ditertiary-butyl peroxide, isopropyl cyclohexyl peroxide, dicumyl peroxide, and tertiary-butyl cumyl peroxide. These peroxides, as well as others, are wellknown for their utility in producing free-radicals which effect the crosslinking of polymers, such as polydiolefins, polyolefins, polyesters, and various copolymers. However, the latter two peroxides inevitably also produced a lingering, objectionable odor of acetophenone in the crosslinked polymer. As a result polymers crosslinked in this fashion were restricted to areas of use where such odors were tolerable, e.g. wire coating for outdoor applications.

It has now been found that if the aryl nucleus of a tertiary-alkyl cumyl peroxide is substituted with one or more halogens two surprising improvements are obtained; namely, (1) there is no objectionable odor when used to crosslink polymers, and (2) the crosslinking efficiency of the halo-substituted peroxide is greater than that of the unsubstituted peroxide.

The halogenation of di-t-butyl peroxide to give halogenated peroxides is well-known (see e.g. US. Pat. No. 2,501,966 and US. Pat. No. 3,169,103) generally producing a mixture of symmetrical and unsymmetrical halo peroxides containing from one to four halogen atoms. Isolation of anyone of these compounds is difficult since, for example, there are three dichloro isomers, five trichloro isomers, and nine tetrachloro isomers. Pure monohalo-di-t-butyl peroxides have been prepared by the alkylation of the monohalo-t-butyl hydroperoxide with t-butyl alcohol as disclosed in US. Pat. No. 2,501,967. The preparation of bis(pchlorocumyl) peroxide and bis(3,4-dichlorocumyl) peroxide has been disclosed in British Pat. No. 961,481; and dibromo-dialkyl peroxides have been disclosed in US. Pat. No. 3,304,332. None of these references, however, discloses or suggests the tertiary-alkyl halocumyl peroxides of this invention nor the advantages achieved by these novel peroxides.

It is an object of this invention to provide novel tertiary-alkyl halocumyl peroxides. It is another object of this invention to provide cumyl peroxides which are efficient crosslinking agents and yet which do not produce any objectionable odor during the crosslinking. Still other objects will become apparent from the detailed description of this invention.

The novel peroxides of this invention are especially useful as crosslinking or curing agents. These' peroxides are halogenated derivatives of t-butyl cumyl peroxide, the halogen substituents being attached to aromatic nuclear carbon atoms. These compounds are especially valuable for crosslinking or curing polymers where objectionable odors that are usually associated with peroxide-cured polymers cannot be tolerated. The decomposition by-products of these peroxides leave no objectionable odors in the crosslinked or cured polymer. Moreover these novel peroxides are more efficient as crosslinking agents than unsubstituted .t-alkyl cumyl peroxide, although the explanation of thisunexpected improved efficiency is not entirely understood. It may be because the peroxides of this invention have higher boiling points than the unsubstituted peroxide and that less peroxide is lost by volatilization during incorporation of the peroxide into the molten polymer by milling or Banburying. However, alkyl-substituted tbutyl cumyl peroxides which are less volatile than the unsubstituted compound are also less efficient than the halocumyl peroxides of this invention. Therefore, the increased efficiency of these novel peroxides cannot be attributed solely to higher boiling points.

The novel compounds of this invention are tertiaryalkyl halocumyl peroxides of the formula:

wherein X is fluorine, chlorine, or bromine; R is hydrogen, alkyl, cycloalkyl, or aryl; R is a tertiary-alkyl or 4-8 carbon atoms; and n is an integer from 1 to 5. 1n the preferred embodiments of this invention the aromatic nucleus is substituted l-3 times with halogen and the remaining substituents are hydrogen or lower alkyl, and the tertiaryalkyl group is tertiary-butyl or tertiaryamyl. Thus, the preferred peroxides have the formula:

wherein X is fluorine, chlorine, and bromine; R is hy: drogen or lower alkyl of 14 carbon atoms; R is tertiary-butyl or tertiary-amyl; and m is an integer from 1 to 3.

In the foregoing formulae R may be alkyl, cycloalkyl, or aryl. Included among these substituents are methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl, octyl, and decyl, including the primary, secondary, and tertiary forms of these alkyls. The lower alkyls of l4 carbon atoms are preferred, i.e. methyl, ethyl, propyl, butyl, isopropyl, sec.-butyl, and tert.-butyl. lncluded among the cycloalkyls and aryls are cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl, phenyl, benzyl, naphthyl, and the like. It is to be understood that any of the foregoing may be further substituted with inert substitutents, such as halogen.

R is a tertiary-alkyl of 4-8 carbon atoms, which means that the alkyl group has 4'8 carbon atoms, at least one of which is a tertiary carbon atom through which the alkyl group is attached to the peroxide group. Therefore the tertiary-alkyl group may be tertiary-butyl, tertiaryamyl, tertiary-hexyl, tertiary-heptyl, or tertiary-octyl. It is unimportant whether the tertiary carbon atom of the tertiary-alkyl is the only tertiary carbon atom in the molecule or where that tertiary carbon atom is located in the molecule so long as a tertiary carbon atom is attached to the peroxide group. Thus. in addition to l,1-dimethylbutyl. tertiary-hexyl includes 2-methylpentyl, 3-methylpentyl, and 1.1.2- trimethylpropyl. Tertiaryheptyl includes 1.1- dimethylpentyl. Z-methylhexyl, 3-methylhexyl, 1.1,2- trimethylbutyl. 1,1,3-trimethylbutyl, 1.1.4- trimethylbutyl, 1.1,2,2-tetramethylpropyl. 1 ,1 ,3.3-tetramethylpropyl. and l,1-dimethyl-Z-ethylpropyl. Tertiary-octyl includes 1 ,1.2,3,3pentamethylpropyl, 1, 1 .3,3-tetramethylbutyl, 1,1,2,2-tetramethylbutyl, 1.1,2-trimethy1pentyl,. 1,1,3-trimethylpentyl, 1,1,4- trimethylpentyl. 2,3.4-trimethylpentyl, 1, l dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2,5-dimethylhexyl, and 3,4-dimethylhexyl. 2- methylheptyl, 3-methylheptyl, 4-methylheptyl, 2,3- diethylbutyl. 2-methyl-3-ethylpentyl, 2-methyl-4- ethylpentyl, 3-ethylhexyl, etc. These tertiary-alkyl groups are preferably hydrocarbons but they may in less preferred embodiments be substituted with inert groups such halogen.

Among the preferred tertiary-alkyl haloeumyl peroxides of this invention are those in Table I which refers to the generic formula above.

Table 1 Substituents in Formula Name R X n Hydrogen t-Butyl Chlorine 1 t-Butyl Z-chloroeumyl peroxide Hydrogen t-Butyl Chlorine l t-Butyl 3-chlorocumyl peroxide Hydrogen t-Butyl Chlorine 1 t-Butyl 4-chloroeumyl peroxide Hydrogen t-Amyl Chlorine 1 t-Amyl 3-chlorocumyl peroxide Methyl tButyl Chlorinc 1 t-Butyl S-chloromethylcumyl peroxide Hydrogen tButyl Chlorine 2 t-Butyl 3,4-dichloroeumyl peroxide Hydrogen t Butyl Chlorine 3 t-Butyl 2.3.6

trichlorocumyl peroxide Hydrogen t-Butyl Bromine 1 t-Butyl 4-bromoeumyl peroxide Ethyl t-Butyl Bromine l t-Butyl 4-ethyl-2- bromocumyl peroxide lsopropyl t-Butyl Bromine 2 t-Butyl 4-isopropyl-3.

o-dibromocumyl peroxide Hydrogen t-Butyl Fluorine l t-Butyl 4-fluoroeumyl peroxide Hydrogen t-Butyl Fluorine l t-Butyl 3fluoroeumyl peroxide Hydrogen t-Butyl Fluorine 1 t-Butyl Z-fluoroeumyl peroxide lsopropyl t-Amyl Fluorine 1 t'Amyl 4-isopropyl-2- fluorocumyl peroxide Butyl t-Butyl Chlorine l t-Butyl 4-hutyl-2- chloroeumyl peroxide t-Butyl & t-Butyl Chlorine 3 t-Butyl 4-tbutyl-2- Methyl methyl-3.5,6

triehlorocumyl peroxide Methyl t-Amyl Bromine 2 t-Amyl 2.4-dimethyl-3.6- dibromoeumyl peroxide Hydrogen t-Oetyl Chlorine 1 1.1.3 .3 tctramethylbutyl 4 chloroeumyl peroxide The compounds of this invention may be prepared by a variety of known chemical reactions such as (1.) the acidcatalyzed condensation of the appropriately substituted cumyl alcohol and t-alkyl hydroperoxide; (11.) electrophilic halogenation of t-alkyl cumyl peroxide; (111.) the transition metal catalyzed decomposition of t-alkyl hydroperoxide in the presence of a suitably sub- LII 6 stituted eumene; and (IV.) the process of parent application Ser. No. 771,344 involving the addition of talkyl hydroperoxide to a suitably substituted a-methylstyrene in the presence of a catalytic amount of a similarly substituted cumyl halide.

Reactions represented by 1., 111., and IV. are preferred if an isomer-free product is desired.

The tertiary-alkyl haloeumyl peroxides of this invention are effective crosslinking (vulcanizing) agents for polymeric materials which are capable of being crosslinked to form a thermoset material. Herein the words of art crosslinking and vulcanizing are used as synonyms.

According to the present invention there is provided an improved method for the crosslinking of filled or unfilled polymeric materials which method comprises heating said polymeric material, and an amount of tertiary-alkyl haloeumyl peroxide sufficient to achieve the desired degree of crosslinking. The preferred amount of peroxide is from about 0.004 to about0.02 equivalents based on the polymeric material to be crosslinked. The improved method essentially eliminates the blooming and/or odor problems associated with the use of prior art aralkyl peroxide crosslinking agents. 7

These polymeric materials include those natural and synthetic materials which are thermoplastic or have indefinite melting points and which can be transformed to thermoset materials-elastic, or more or less rigid solids-by a crosslinking (curing) reaction, through the action of an added agent.

Illustrative classes of operable polymeric compounds are: The solid polyolefins such as polyethylene; and polybutenes. The elastomers such as natural rubber and the synthetic rubbers including butyl rubber, GR-S rubber, neoprene, acrylic rubber, Buna rubber, ethylene-propylene rubber and the silicone rubbers and miscellaneous elastomers such as polybutenestyrene copolymers, and urethane rubber. The polymers may contain plasticizers and/or oil extenders.

An intimate mixture of the defined polymeric material and the tertiary-alkyl halocumyl peroxides of this invention can be stored until needed. The mixture can be heated cured in reasonable times at reasonable temperatures to a crosslinked (vulcanized) material. The temperature and time are controlled, and sufficient agent used to afford the desired degree of crosslinking at these conditions.

In addition to the defined polymeric material and the tertiary-alkyl halocumyl peroxide in intimate mixture, the crosslinkable composition may contain co-agents such as sulfur, promoters, coupling agents, fillers, reinforcing materials, and any other materials conventionally used in the production of a crosslinked composition. Desirable fillers are carbon blacks, titanium dioxide, calcium silicate, and the alkaline earth metal carbonates. Neutral or alkaline carbon blacks are the preferred carbon blacks.

The crosslinkable composition is heat cured for a time sufficient to obtain the desired degree of crosslinking. The heat curing has a temperature-time relationship which is primarily dependent on the polymeric material and the peroxide present but is affected by the formulation as a whole. It is customary to use a time equal to about 6-8 half-lives of the peroxy agent.

It has been discovered that crosslinked polymeric compositions prepared using the tertiary-butyl halocumyl peroxides of this invention essentially do not develop a bloom on aging and exhibit no residual odor caused by the decomposition of the peroxide.

Embodiments of crosslinkable (vulcanizible) compositions, crosslinked (vulcanized) compositions, and the heat curing thereof are set out in certain of the following examples.

In general, the ingredients of these formulations are milled to an intimate plastic mixture on a standard roll mill, such as used in the rubber industry. The temperature of the mix during milling is held below 250F. At these conditions no scorching occurs.

The imtimately mixed vulcanizable mass is removed from the roll mill and a portion placed in a mold in a hydraulic press and heat cured. The curing times and temperatures are varied depending upon the peroxy crosslinking agent and the polymeric material used.

Immediately upon removal from the curing press, the cured slabs are permitted to mature at room temperature for about 24 hours. This maturing time is sufficient to give reproducible results.

The matured slabs are then cut into dumbell shaped specimens and tested for tensile strength on an Instron Tensile Tester, following ASTM procedure as prescribed in D412-61T, Tension Testing of Vulcanized Rubber."

The target of commercial quality cured EPR composition is a 300% modulus of 1500:100 p.s.i.

Various embodiments of this invention are illustrated in the following examples although it is not intended that the invention be limited thereby. Parts and percentages are by weight and temperatures in degrees Centigrade unless otherwise indicated.

EXAMPLE 1 t-Butyl p-chlorocumyl peroxide p-Chlorocumyl alcohol was prepared by the addition of methyl-magnesium bromide to pchloroacetophenone. The yield of alcohol was 29%; it boiled at 83C at 0.06 mm. and melted at 42C. The low yield was due to partial dehydration of the alcohol during distillation.

A jacketed, open-top reactor was equipped with a paddle stirrer, thermometer and addition funnel. Into the reactor was charged 14.0 g. (0.1 mol) of 70% sulfuric acid and 15 ml. of methylene chloride. The stirred mixture was then cooled to 5C by passing iced brine through the reactor jacket. To the cooled mixture was slowly added 13.5 g. (0.15 mol) of t-butyl hydroperoxide. The temperature was not allowed to rise about 5C. To this mixture was added 17 g. (0.1 mol) of p-chlorocumyl alcohol at -5 to 3C over a 30 minute period. The reaction mixture was then stirred an additional 5 hours at 0C and 3 hours at ambient temperature. The reaction mixture was then washed with 50 ml. portions of 10% aqueous potassium hydroxide solution until it was free of unreacted hydroperoxide, then with 50 ml. portions of water until the aqueous phase was no longer alkaline. The organic layer was dried (magnesium sulfate), filtered and stripped in vacuo leaving a colorless organic liquid weighing 24 g. and assaying 97.2% by chlorine analysis and vapor phase-chromatography. Yield (corrected for assay) was 96.5%. The refractive index was 1.4856 at 25C.

This compound was also prepared from p-chloro-amethylstyrene (b.p. 548 and 2 mm.; m, 1.5536) and t-butyl hydroperoxide in the presence of 14 mole of a,p-dichlorocumene. The yield (corrected for assay) was 51%.

These peroxides cannot be assayed by conventional iodometric procedures. 7

EXAMPLE 2 t-Butyl m-chlorocumyl peroxide EXAMPLE 3 t-Butyl P-fluorocumyl peroxide A mixture of 18.4 g. (0.175 mol) of 86% t-butyl hydroperoxide, 3.28 g. (0.019 mol) of p-fluorocumyl chloride and 17.85 g. (0.131 mol) of p-fluoro-amethylstyrene (Baker Chemicals) was stirred at 25C for 20 hours. The reaction mixture was diluted with 30 ml. of ether and washed with two 30 ml. portions of 10% potassium hydroxide solution and 100 ml. of 5% sodium chloride solution. The organic layer was added to 200 ml. of water and the mixture distilled at 50-60 mm. of pressure and 60C until no further oil came over with the aqueous distillate. The organic residue was separated, dried (magnesium sulfate) and filtered.

The residue weighed 24.2 g. and the refractive index was 1.4650 at 22C. The compound had only a single peak in a vapor chromatogram. chromtogram, and assayed 97% (based on fluorine content). The yield (corrected for assay) was 71.5%.

EXAMPLE 4 t-Butyl 3,4-dichlorocumyl peroxide 3,4-Dichlorocumyl alcohol was prepared in 99% yield from methylmagnesium bromide and 3,4- dichloroacetophenone. The alcohol was not distilled because it was very susceptible to dehydration. It was judged to be free of starting ketone by the absence of a carbonyl absorption in its infrared spectrum.

' Into a jacketed, open-top reactor, equipped with mechanical stirrer, thermometer and addition funnel was placed 35 g. (0.25 mol) of 70% sulfuric acid and 75 ml. of methylene chloride. The stirred mixture was cooled to 8 and 30 g. (0.33 mol) of 98.3% t-butyl hydroperoxide was added dropwise at such a rate that the temperature did not rise above 5C. Then 50 g. (0.244 mol) of 3,5-dichlorocumyl alcohol was added over a 40 minute period keeping temperature at -5C. Mixture wasthen stirred for 90 minutes at to +C. and then for 30 minutes at 510C.

To the reaction mixture was added 50 ml. of ether and 50 ml. of ice water. The acidic aqueous layer was drained off. The organic layer was dried (magnesium sulfate). filtered and stripped in vacuo. The residue weighing 57 g. contained a considerable amount of unreacted alcohol (according to an infrared spectrum). The crude product was again treated with 70% sulfuric acid (35 g.) and t-butyl hydroperoxide (30 g.) as above but was stirred 90 miunutes at 0l0C and 90 minutes at l015C and hours at l518C. After the usual work-up, the dried organic solution was stripped in vacuo at 45-50C at an ultimate pressure of 0.05 mm.

, The residue was a yellow oil weighing 27.6 g. and assaying 97.3% (based on chlorine analysis). The yield (corrected for assay) was 41%.

EXAMPLE 5 t-Butyl p-bromocumyl peroxide p-Bromocumyl alcohol was prepared in 50% yield from methyl-magnesium and p-bromoacetophenone. The alcohol melted at 368C.

The peroxide was prepared in the manner described in Example 1 from 70% sulfuric acid, 93% t-butyl hydroperoxide and p-bromocumyl alcohol. The product assayed 99.6% (bromine analysis) and its refractive index was 1.5013 at 25C. The yield (corrected for assay) was 96.3%.

EXAMPLE 6 t-Butyl chlorocumyl peroxide A 100 ml., 3-necked flask was equipped with a thermometer, magnetic stirrer, a dry ice-isopropyl alcohol reflux condenser and a gas inlet tube.

Into the flask was charged 20.8 g. (0.1 mol) of t-butyl cumyl peroxide and 25 ml. of carbon tetrachloride. The mixture was stirred at 5C while 8.5 g. (0.12 mol) of gaseous chlorine was bubbled in over a 25 minute period. The mixture was stirred at 0C for minutes, then the reaction mixture was stripped in vacuo at 0C in order to remove unreacted chlorine and hydrogen chloride. The yellow liquid residue was dissolved in ml. of ether and washed with 50 ml. of 10% potassium hydroxide solution and five times with 50 ml. portions of 10% sodium carbonate solution. The organic layer was dried (magnesium sulfate), filtered and stripped in vacuoto give 21.1 g. of a pale yellow oil; n 1.4850 (t-butyl cumyl peroxide, n 1.4767; t-butyl pchlorocumyl peroxide, 11,, 1.4865; t-butyl mchlorocumyl peroxide, n 1.4886). The product contained 68% of the theoretical chlorine for a monochloro derivative. A vapor phase chromatographic analysis indicated the presence of t-butyl pchlorocumyl peroxide along with unreacted t-butyl cumyl peroxide and other chlorinated peroxides.

EXAMPLE 7 Half-Lives of t-Butyl halocumyl peroxides In Table 11 are listed the half-lives of selected peroxides. The determinations were carried out on 0.2 molar solutions of the peroxide in benzene. The decomposition was followed, in most cases, by withdrawing samples periodically from a thermostated bath and determining the amount of undecomposed peroxide by vapor phase chromatography. The half-life of t-butyl cumyl peroxide is included for comparison purposes.

TABLE I1 Half-Lives of Peroxides in Benzene at l 15C in hours.

t-Butyl cumyl peroxide 17.2 t-Butyl p-chlorocumyl peroxide 20.2 t-Butyl m-chlorocumyl peroxide 18.0 t-Butyl 3.4-dichlorocumyl peroxide 19.3

t-Butyl p Fluorocumyl peroxide 18.8 t-Butyl p-bromocumyl peroxide 18.8

As can be seen in Table II the presence of the aromatic halogen seems to slightly raise the thermal stability of the non-halogenated peroxide.

EXAMPLE 8 Curing of Polyester Resin The halogenated peroxides were elevated as hightemperature curing agents for Basic Polyester Resin having the following formulation:

Maleic anhydride moles 1.0 Phthalic anhydridc do 1.0 Propylene glycol do 2.2 Acid number of alkyd resin 35-45 Inhibitor (hydroquinone) (percent of final solution) percent 0.013 Styrene monomer (percent of final solution) do 30 The catalyst concentration was 1% by weight of resin. The standard S.P.l. exotherms were determined at l 15C and the resulting data are summarized in Table [II where it can be seen that the peroxides of this invention are somewhat slower than dicumyl peroxide but are equivalent in all other respects and, significantly,

do not leave an unpleasant, persistent odor in the cured resin as dicumyl peroxide does.

TABLE 111 Peroxiee Curing of Polyester Resin at l 15C t-Butyl t-Butyl p-chlorom-chloro- Dicumyl cumyl cumyl peroxide peroxide peroxide (iel timc(min.) 6.5 7.6 7.8 Cure timc(min.) 7.9 9.6 9.6 Peak Exotherm(F) 445 435 440 Barcol Hardness 45 45 45 EXAMPLE 9 vulcanization of Ethylene-propylene rubber Selected peroxides were compounded with ethylene-' propylene rubber using 10 milliequivalents of peroxide per 100 g. of rubber. Test pieces were vulcanized in a heated platen press at 320, 340 and 375F. The tensile properties of the vulcanized rubbers are summarized in Table IV from which it can be seen that the peroxides of this invention are equivalent to dicumyl peroxides, a wellknown vulcanization agent; however, the test pieces, vulcanized with the peroxides of this invention did not have the objectionable odor of acetophenone which was present in the test pieces vulcanized with dicumyl peroxide.

TABLE V Crosslinking of Polyethylene* I 70 crosslinked Cure Temp.F

Peroxide 320 1 340 375 t-Butyl cumyl peroxide 82.0 85.0 i 84.8 t-Butyl p-methylcumyl peroxide 79.1 81.3 80.3 t-Butyl p-isopropylcumyl peroxide 81.4 82.2 81.4 t'Butyl p-chlorocumyl peroxide 85.1 88.4 87.5 t-Butyl m-ehlorocumyl peroxide 84.2 87.8 86.9 t-Butyl 3,4-dichloroeumyl peroxide 84.2 87.8 88.5 dicumyl peroxide 90.5 89.9 89.0

The polyethylene was Bakelite DYNH-l made by Union Carbide Plastics Division. The polyethylene charge had zero erosslinking.

TABLE IV vulcanization of Ethylene-Propylene Rubber* Cure Temp. t-Butyl-pTluorocumyl t-Butyl-3,4-diehloro- "F Dicumyl Peroxide (Tech.) peroxide cumyl peroxide 300% M. U.T.S. 7? E 30071 M. U.T.S. 7: E 30071 M. U.T.S. 71 E lbs./sq.in. lbs./sq.in. lbs./sq.in.

M modulus U.T.S. ultimate tensile strength E elongation *The formulation of the Ethylene-Propylene Rubber used is EPR 404 (40:60 ethylenezpropylene content; no oil extender;

made by Enjay Chemical Co.) 100 parts SRF carbon black 60 parts Sulfur 0.3 parts EXAMPLE 10 CH,

Crosslinking of Polyethylene The peroxide (usually 0.01 equivalents of peroxide per 100 g. of polyethylene) was milled into DYNH-l, RM

a grade of low-density polyethylene, on a two-roll mill. The milled sheet was cut into plaques and cured in a platen press at a ram pressure 20,000 psi. for 30 minutes at the temperature specified. The percentage of crosslinking was determined by extracting the unerosslinked portion with xylene at 80C.

The data for selected peroxides are shown in Table V. Data for t-butyl cumyl peroxide and for t-butyl palkyleumyl peroxides are shown for comparison purposes. It can be seen that the peroxides of this invention are superior to t-butyl cumyl peroxide and also to tbutyl alkylcumyl peroxides of similar molecular weight. In addition, there is no unpleasant odor from peroxide decomposition products as there is with t-butyl cumyl peroxide or dicumyl peroxide.

wherein X is fluorine, chlorine or bromine; R is hydrogen, alkyl, cycloalkyl or aryl; R is a tertiary-alkyl radical of 4-8 carbon atoms; and n is an integer from 1 to wherein X is fluorine, chlorine or bromine; R is hydrogen, alklyl, cycloalkyl or aryl; R is a tertiary-alkyl radical of 4*8 carbon atoms; and n is an integer from lto 5.

3. rnethodof claim 1 wherein a filler is present in said polymeric material.

4. The method of claim 1 wherein the polymeric material ispolyethylene, ethylene propylene rubber, or

unsaturated polyester resin.

5. The method of claim 1 wherein said peroxide is tertiary-butyl chlorocumyl peroxide.

6. The composition of claim 2 wherein a filler is present. 

1. THE METHOD OF CROSSLINKING A CURABLE COMPOSITION COMPRISING HEATING A MIXTURE OF A FREE RADICAL CROSSLINKABLE POLYMERIC MATERIAL AND A CROSSLINKING AMOUNT OF AN ORGANIC PEROXIDE AND RECOVERING CROSSLINKED POLYMERIC MATERIAL, THE PEROXIDE BEING OF THE FORMULA
 2. A CROSSLINKABLE COMPOSITION COMPRISING A FREE RADICAL CROSSLINKABLE POLYMERIC MATERIAL AND A CROSSLINKING AMOUNT LF A PSROXIDE OF THE FORMULA
 3. The method of claim 1 wherein a filler is present in said polymeric material.
 4. The method of claim 1 wherein the polymeric material is polyethylene, ethylene propylene rubber, or unsaturated polyester resin.
 5. The method of claim 1 wherein said peroxide is tertiary-butyl chlorocumyl peroxide.
 6. The composition of claim 2 wherein a filler is present.
 7. The composition of claim 2 wherein the polymeric material is polyethylene, ethylene-propylene rubber, or unsaturated polyester resin.
 8. The composition of claim 7 wherein the peroxide is tertiary-butyl p-chlorocumyl peroxide.
 9. The method of claim 1 wherein the polymeric material is polyethylene or ethylene-propylene rubber.
 10. The composition of claim 2 wherein the polymeric material is polyethylene or ethylene-propylene rubber. 